Azo dyestuff from barbituric acid and process of making the same



P tented Nov. 9,1926,

GUILLA ME DE MONTMOLLIN, FRITZ STRAUB, AND JOSEPH SPIELER, or BASEL, SWITZERLAND,- ASSIGNQRS TO SOCIETY or cnnnucar. INDUSTRY IN BASLE, or

BASEL, SWITZERLAND.

AZO DYESTUFF FROM 'IBAIRBI'IIJ'RIC ACID D PROCESS OF MAKING THE SAME.

No Drawing. Application filed December 1, 1925, Serial No. 72,579, and in Switzerland December 24, 1924.

wherein R stands for a hydrogen atom an alkyl, aryl or aralkyl residue and n for a whole number not higher than 2, may be I combined with ortho-hydroxydiazo compounds. There are thus obtained new mordant dyestuifs, which form yellowto brownish-red powders, dissolving in dilute sodium carbonate solution with yellow to brownish red coloration and dyeing wool in an acid bath yellow to red and brown tints which may change to brown and to red by afterchroming yielding thus tints fast to milling and potting, and very fast to light. The dyestuffs correspond withthe general formula:

- 0 H ti --i-r Rr- -N 0:0

I o c n wherein R stands for a hydrogenatom, an alkyl, aryl or arallryl residue, n for a whole -nmnber not higher than 2, and R for an aromatic residue carrying an OH-group in ortho position to the azobridge. The value of these new dyestuffs, however, resides in the factof thei convertibility into new acid dyestuffs by treatment with agents yielding chromium suclr as the oxides, hydroxides or salts of the trivalent chromium, forming ,thus in a dry state, yellow to dark-brown and black powders, dissolving in Example 1.

introduced into a mixture' carbonate solution to yellow-brown, red and pink solutions, and dyeing .wool in an acid bath level and fast yellow to orange, brown and red or pink tints.

The barbituric acids employed in the present invention may be prepared quite generally by condensing urea or. the ureas of the general formula R-(NH.CO.NH,) n, wherein R stands for alkyl, aralkyl and aryl residues, and nfor a whole number not higherthan 2, with esters of the malonic'acid.

In th1s manner there may be obtained from the correspondmg ureas amongothers the following barblturic acids:

Melting point, or temperature oi decomposition.

Urea. Barbituric acid. 4 w i Recrystal- Raw lized fromproduct. glacial acetic acid.

I. Phenylurea.-- Phenylbarbituric' I 264 266 I am IL o-Tolylurea o-Tqlylbarbituric 244 246 aci III. p-Toly1urea ,p-Tciiilylbarbituric 244 245 ac IV. p-Chlorophenylp-Chlorophenyl- 236 238 urea. barbituric acid. 1 V. o-Methoxyphenylo-Methoxyphenyl- 263 263 urea. barbituric acid. VI. in- Nitrophenylm Nitrophenyl- 216 224 urea. barbituxic acid. VII. p-Nitrophenylp Nitrophenyl- 262 264 urea. barbituric acid. VIII. a 7 Naphthyla Naphthylbar- 233 236 urea. bituric acid. IX. fl-Naphthylurea. B Naphth'ylbat- 245 246 bituric acid. X, o-Carboxyphenylo-Carboxy'phenyl- 267 276 urea. barbituric acid. XI. 4 Hydroxy 3 4 Hydroxy-3-ear- 260 272 carboryphenylurea. boxyphenylbarbituric acid. XII. p-Ammophenylp Aminophenyl- Above300 Above 300 urea. barbituric acid. XIII. D1pheny1-4,4 Diphenyl-4,4 di- Above 300 Above300 d urga (from benzlbarbituric acid.

ne I XIV.'3,3 Ditolyl 3,3 Ditolyl-4, 4'- Above 300 Above 300 4, 4- diurea (from dibarbituric acid. tolidme).

The barbiturid acid derived from the urea.

dilute sodium, number XIII corresponds with the formula o n v i l lution of 30% strength,-170,parts of sodium carbonate and 1500 parts of water. Coupling- 233 parts of 4-su1fo-2-amino-1phenol 6- takes place immediately; In order to activate caiboxylic acid are diaz'otized as usual and the latter the whole is stirred for some time.

of134 parts of The dyestufl' thus obtained is then filtered. barbituric acid, 133 parts of caustic soda so- It f i dry state, an orange powder,

dissolving in water to a yellowish-orange solution by addition of sodium carbonate solution, and dyes wool, from an acid bath, yellow tints changing to brownish-yellow and becoming fast by afterchroming. The

'dyestuff corresponds most probably with the following formula:

\0 H/ OH 900E A i I=N 0 H Example 2.

CgHr-N 0:0 0 H H coo O|H Emmple 3.

- 224 parts of 4-chloro-2-amino-1-phenol- 5-sulfonic acid are diazotized as usual and introduced into a solution of 230 parts of benzylbarbituric acid, 140 parts of caustic soda solution of 30% strength,.2000 parts of water and 100 arts of carbonate of soda. After some time he formation of the dyestufl is accomplished, it is filtered and dried.

. is filtered and dried.- It forms a brown powder, dissolving in dilute sodium carbonate solution with yellow coloration and dyemg w ool from an acid bath orange tints changing to brown byafterchroming.

Example 6.

32,8 parts of the dyestuff made from diazotized 2-amino-1-phenol-4c-sulfonic acid 100 and barbituric acid are dissolved in 650 parts of boiling water and treated with a soution of chromium formate corresponding The dyestufi forms a brown powder and dyes wool from an acid bath yellowishbrown tints changing to brick-red by afterchroming. The dyestuff corresponds very probably with the following formula:

224 parts of 4-chloro-2-amino-l-phenol-5- sulfonic acid are diazotized as usual and introduced into a solution from 214; parts of phenylbarbituric acid, 135 parts caustic soda solution of 30% strength and 100' parts of sodium carbonate in 2000 parts of water. Coupling occurs instantly and after some stirring the whole diazo compound has disappeared. The dyestufi' thus obtained is then salted out as usual, filtered and dried. It forms a red-brown powder, dissolving in water by addition of sodium carbonate with orange coloration and dyeing wool from an acid bath yellow tints changin to orange by afterchroming. The dyestu corresponds very probably with the following formula:

0 n CuHr-N C=O 6H ocn ti 1- 1- N son:

1 Emmnple 5.

154 parts of 4-nitro-2-aminophenol are diazotized as usual and introduced into an aqueous solution containing 203 parts ,of diphenyldibarbituric acid, 250 parts of sodium carbonate and 2000 parts of water. Coupling occurs rapidly and the dyestufi' thuls obtained corresponding with the formu a:

o, with 15,2 parts of Cr O The Whole is boiled for some hours in a reflux apparatus, partly evaporated and the new chromium compound isolated as usual. It forms a brown powder, dissolving in dilute sodium carbonate solution with yellow coloration,

and dyeing wool from an acid bath fast reddish-yellow tints.

Example .7.

100 parts of a chromium hydroxide paste corresponding with 12,3 parts of C150,, 28

carbonate solution with yellow coloration,

Mordant dyestufl. Chromium compound.

o-Hydroxyamino Barbltlmc acid compound. Color of Color in Acid Alter- D estufl Color in Color of the dry dilute soda d ein chromed oywder dilute soda acid dyeing dyestufl. solution. y dyeing. p solution. on wool.

I I. Barblturic acid 2-An ino-l-phenol-4-sul- Brown. Y cl lo w- Ycllow Brown- Brown. Yellow.-." R e do is hlonic acid. orange. yellow. yellow. 6-Nltro-2-am in0-1- Yellow Yollow- Brown- Yellow- Orange- Reddisliphenl-4 sullon c acid. orange. yellow. brown. yellow. yellow. III. Barbituric acid 4-Cliloro-2-arnino-l- Yellow- Yellow- Yellow Brown- Yellow- Orange Reddishpl gnol-fi-carboxyh brown. orange. orange. brown. yellow.

. aci IV. Barbituric acid 4-N itro-2-amin0-1- Yellow- Yellow- 13 rown- Brow-11.- Brown... Yellow.... 13 r o w n phenolbrown. orange. yellow. 1 orange. V. Barbituric acid 4-cliloro-2-amino-1- Brown.. Yellow- Yellow Brown- Brown Yellow--. Orange.

p en orange. orange. VI- B rb t 861d p -P Brown.. 0range. Reddish- Yellow- Brown Reddish- Y e i l o w fam de. yellow. brown. yellow.- orange. VII. Barbitimc acid----- l-a m in 0-2-11 y d r 0 y- Brown- Red Brown..." Brown.. Reddisli- Pink Pink.

naphthalene-l-sulbr wn. lonic acid. VIII. Barbituric acid.... Nitrated diazo c0m- Brown-. B r o w n- Brown. Brown" Brown..-.- Or a n g e Red.

A pound of 1-amino-2- red. red.

hydroxynaphthalenea 4-si1lfonic acid. 1X- Pl18I1Y1b8rblt11I10 2- mi -1-D w 1 1- R e d Orange-. Yellow Brown- Brown. Yellow.---. Re d dishacid. ionic acid. brown. yellow. yellow. l y fi 4chloro2-amino- 1-phe- Brown.. Orange Yellow Orange- Brown Y a ll 0 w R e d dish ac nol-5'su1fonic acid. orange. orange. XI. Phenylbarbrturic 4-niti-o-2-amino-I-phe- R e d Yellow.--- Orange.--" Yellow Brown..- Yellow..... Y e l l o w aci nobo-sulfonic acid. brown:- orange. X Phenylbarbltunc -S -Ph Orange Y ellow- Yellow"--- Yellow Brown.-- Yellow Yellow.

ac nol-6carboxylic amd. orange. L Phenylb arblturw o ydro ynaph- Brown. Red Brown- Red... Blackish- Pink Pink. ac I thalene--sulfonic acid. XIV. Phenylbarbituric Nitrated diazo com- Brown B r o w n- Brown- Brown Brown B r o w n R e d dishacid. pound of 1-amuio-2- red. red. brown.

' hydroxynaphthalene- I I j. 4-sulionic acid. XV. o-Tolyllgarbituric 2-Amino-1 -phenol-4-sul- Brown. Orange Yellow- Brown- Brown. Yellow..... Orange.

acid. fonic acid. b yellow. p-Tolylbarbltllrlc 4:0 h l o r o-2-a mi 11 o-1- Brown- Red Brow 0range Reddisli- Orange--- Red-orange.

acid. phenohfisulfonic acid. brown. XVII. pChloro-plienyl- 4-Nitro-2-aniino-1-phe- Yellow Orange Yellow-or- Yellow- Brown- Ycl1ow-or- Yellow-orbarhituric acid. nol-fi-sulionic acid. ange. brown ange. range. XVIII. o- Methox y-plie- 4-Nitro-2-amino-1-plie- Yellow Yellow Orange".-. Yellow Brown.... Yellow...-... Orange. nylbarbituric acid. nol-fi-sulfonic acid. 7 XIX. p-Nflzro-phenyl- 4-Cliloro-2amino-1-plie- Brown.; Oran ge- Orange-red- 0range Reddisli- 0range Reddish-orbarbituricacid. nol-5-sulfonic acid. red. brown. ange. XX. a- Na phtliylbar- 2-A min o-l-p h e 11 01-4- Brown 0 r a ng e Brownish- Orange Brown. Red-orange. Red-orange.

bituric acid. choloro-5-sullonic aid. red. yellow. XXI. fi N aphthylbar- -Nitrn-z-ainino-l-phe- Orange Yellow.... Yellow-or Brown- Yellowish- Yellow R e d dishbitnric acid. nol -6-sullonie aoid. ange. yellow. brown. yellow. XXII. 4-Hydroxy-pl1e- 6-Nitro-2-amino1-phe- Brown-. 0range Red..- Brown. Brown. Brownish- Brownisln pyrlli-cairb oxy-barbinol-d-sulfonic acid. 4 orange. orange.

dyeing wool from an acid bath reddish-yellow tints.

Eazample 8.

in dilute sodium carbonate solution with yellow-orange coloration, dyeing wool from an acid bath -fast orange tints.

Example .9.

43,8 parts of the dyestuft' made from diazotized 4-chloro-2-amino-1-phenol-5-su1- fonic acid and barbituric acid are dissolved in 800 parts of a solution of chromium ange coloration, dyeing wool from an acid bath fast orange tints.

In an analogous manner there may be ob tained yellow to red and brown dyestufls containin chromium from further o-hydroxyazo yestufis derived from other barbituric acids.

The following table gives the properties i of some of the dyestuffs of the present invention and of the corresponding mordant dyestuffs:

The dyestufi number VIII corresponds with the formula:

t t=N lhe dyestuif' number XX corresponds with the formula:

1L=NQSOuH l i What we claim is:

1. As step in the production of new acid dyestuffs the herein described coupling of the barbituric acids corresponding with the generalformula:

wherein R stands for a hydrogen atom, aryl, alkyl or aralkyl residues and 'n, for a 'whole number not higher than 2, with o-hydroxy diazo compounds.

2. As step in the production of new acid .dyestufls the herein described coupling of the barbituric acids corresponding with the general formula:

wherein R stands for a hydrogen atom, aryl, alkyl or aralkyl r@idues with o-hydroxy diazo compounds.

3. As step in the production of new acid dyestuffs the herein described treatment of mordant dyestuffs corresponding with the general formula:

wherein R stands for a hydrogen atom, aryl, alkyl or aralkyl residues, n for a whole number not higher than 2, and R for an aromatic residue carryin an OH-group in ortho-position to the azo ridge, with compounds of trivalent chromium.

meaeoe 4. As step in the production of new acid dyestufis the herein described treatment of mordant dyestuffs corresponding with the general formula:

wherein R stands for a hydrogen atom,

aryl, alkyl or aralkyl residues, and. R foran aromatic residue carrying an (DH-group in ortho-position 'to the azobridge, with compounds of trivalent chromiuin.-

5. As step in the production of new acid dyestufis the herein described treatment of mordant dyestuffs corresponding with the general formula:

wherein R stands for a hydrogen atom, aryl, alkyl or aralkyl residues, and R, an aromatic residue of the'benzene series carrying an OH-group in ortho-position to the azobridge, with compounds of trivalent chromium.

6.. As new products the herein described new chromium compounds, derivatives of the dyestuffs corresponding with the general formula:

wherein R stands for a hydrogen atom,

wherein R, stands for a hydrogen atom,

aryl, alkyl or aralkyl residues, and R for an aromatic residue carryin an OH-group in ortho-position to the azo ridge, which dyestufi's form yellow to brownish-red powders,

dissolving in dilute sodium carbonate solution with yellow to brownish-red and pink coloration, and dyeing wool in an acid bath fast yellow to reddish-orange, pink and brown tints.

8. As new products the herein described new chromium compounds, derivatives of the dyestuffs corresponding with the general formula:

ll iii-R.

aryl, alkyl or aralkyl residues, and R for an aromatic residueof the benzene series carrying an OH-group in ortho-position to the azobridge, which dyestufi's form yellow to brownish-red powders, dissolving in dilute sodium carbonate solution with yellow to brownish red and pink coloration, and dyeing wool in an acid bath fast yellow to reddish-orange, pink and brown tints.

9. Material dyed with the dyestufi's of claim 6.

10. Material dyed with the dyestuifs ofclaim 7.

11. Material dyed with the dyestuifs of claim 8.

In witness whereof we have hereunto signed our names this 21st day of November' 1925.

GUILLAUME DE MONTMOLLIN. FRITZ STRAUB. JOSEPH SPIELER. 

